Rapidly biodegradable emulsified oil for hydraulic support and preparation method thereof

Abstract

The invention discloses a rapidly biodegradable emulsified oil for hydraulic supports, and the raw materials for preparation include, by weight: 2.0-12.0 parts of synthetic ester, 3.0-15.0 parts of surfactant, 4.0-15.0 parts of anticorrosive and rust-inhibiting agent, 2.0-8.0 parts of complexing agent, 1.0-3.0 parts of bactericide, 0.01-0.50 parts of defoaming agent, 1.0-10.0 parts of coupling agent, and 50.0-70.0 parts of deionized water. The present invention can improve the biodegradability of emulsified oil by using isooctyl oleate as synthetic ester, and has good lubricity, and the stability and hydrolysis stability are better than natural animal and plant oils and fats. The combination of glutamic acid diacetic acid sodium salt and methylglycine diacetic acid sodium salt is used as a complexing agent, which can dissolve calcium and magnesium ions in water, disperse the insoluble organic soap that has been formed, protect the stability of emulsified oil, and avoid the precipitation of impurities to affect the normal operation of hydraulic equipment.

Description

Technical Field

[0001] The invention relates to a rapidly biodegradable emulsified oil for a hydraulic support and a preparation method thereof, and relates to C10M, in particular to the field of a mixture of a base material and an additive. Background Art

[0002] my country is a coal-producing country with rich coal reserves. Large hydraulic support equipment is widely used in mines during coal mining. The transmission medium of the hydraulic support is mainly concentrated liquid or emulsified oil, which is mixed with water in a prescribed ratio during use. During use, due to problems such as machine corrosion and wear of sealing materials, the transmission medium will leak to a certain extent, which will pollute the environment. The commonly used base oil in the emulsion is mineral oil, which is mixed with sodium petroleum sulfonate and ethylenediaminetetraacetate. After leakage, it is not easy to decompose in the environment, and has a certain accumulation tendency, polluting the groundwater in the mine environment. The concentrate does not contain base oil and lipophilic surfactant, but the concentrate without base oil has poor lubrication and anti-rust properties for hydraulic equipment, which will cause faster wear of the equipment and abnormal leakage of the transmission medium. The loss of pressure caused by abnormal leakage may also cause safety accidents, reduce the reliability of the equipment, and shorten the service life of the equipment.

[0003] Chinese invention patent CN201510314086.X discloses an emulsified oil for synthetic hydraulic supports and its preparation method, which first synthesizes heavy alkyl benzene sulfonate sodium, a complex of oleic acid and triethanolamine, and a complex of alkylphenol and ethylene oxide, and then reacts them at room temperature and pressure, solving the problem of environmental pollution caused by the heating production process of rosin potassium soap. However, the base oil is mineral oil, which will still cause harm to the environment after leakage. Chinese invention patent CN201611153158.8 discloses a concentrated liquid for fully synthetic hydraulic supports and its preparation method, which abandons the use of mineral oil and is easily degraded after leakage. However, the prepared concentrated liquid has poor lubrication and rust prevention properties, which affects the long-term stable use of the equipment. Summary of the invention

[0004] In order to improve the degradability of hydraulic oil and make the hydraulic oil have good lubrication and anti-rust properties, the first aspect of the present invention provides a rapidly biodegradable emulsified oil for hydraulic supports. The raw materials for preparation include, by weight: 2.0-12.0 parts of synthetic ester, 3.0-15.0 parts of surfactant, 4.0-15.0 parts of anticorrosion and antirust agent, 2.0-8.0 parts of complexing agent, 1.0-3.0 parts of bactericide, 0.01-0.50 parts of defoaming agent, 1.0-10.0 parts of coupling agent, and 50.0-70.0 parts of deionized water.

[0005] As a preferred embodiment, the synthetic ester is obtained by esterification reaction of an organic acid and an organic alcohol, the organic acid is selected from one or a combination of monobasic acids or polybasic acids, and the organic alcohol is selected from one or a combination of straight-chain fatty alcohols, isomeric alcohols, and polyols.

[0006] As a preferred embodiment, the monoacid is selected from C4-C 22 The isomeric alcohol is selected from one or a combination of isooctyl alcohol, isodecanol and isotridecanol.

[0007] As a preferred embodiment, the monoacid is oleic acid, and the isomeric alcohol is isooctyl alcohol.

[0008] As a preferred embodiment, the synthetic ester is isooctyl oleate.

[0009] As a preferred embodiment, the surfactant composition is a combination of anionic surfactants, nonionic surfactants and additives, and the nonionic surfactant is selected from one or a combination of fatty alcohol polyoxyethylene ether carboxylic acids, fatty alcohol polyoxyethylene ethers, and fatty acid ester polyoxyethylene ethers.

[0010] As a preferred embodiment, the anionic surfactant is fatty acid soap; the additive is triethanolamine; the surfactant is a combination of fatty acid soap, triethanolamine, fatty alcohol polyoxyethylene ether carboxylic acid, fatty alcohol polyoxyethylene ether, and fatty acid ester polyoxyethylene ether.

[0011] As a preferred embodiment, the surfactant is a combination of tall oil fatty acid ALTAPYNE M-28B, triethanolamine, fatty alcohol polyoxyethylene ether carboxylic acid EMULSOGEN COA 070, fatty alcohol polyoxyethylene ether MARLOSOL TA 60, and fatty acid ester polyoxyethylene ether PEG-600DO.

[0012] As a preferred embodiment, the weight ratio of the tall oil fatty acid ALTAPYNE M-28B, triethanolamine, fatty alcohol polyoxyethylene ether carboxylic acid EMULSOGEN COA 070, fatty alcohol polyoxyethylene ether MARLOSOL TA 60, and fatty acid ester polyoxyethylene ether PEG-600DO is (3-5): (3-5): 1: 1 (1-3).

[0013] As a preferred embodiment, the weight ratio of the tall oil fatty acid ALTAPYNE M-28B, triethanolamine, fatty alcohol polyoxyethylene ether carboxylic acid EMULSOGEN COA 070, fatty alcohol polyoxyethylene ether MARLOSOL TA 60, and fatty acid ester polyoxyethylene ether PEG-600DO is 4:4:1:1:2.

[0014] The surfactant system formed by compounding multiple substances has a good emulsifying effect on synthetic esters. The emulsified oil is insensitive to water quality after dilution and has good resistance to hard water. The formed system has stable thermodynamic properties and a high biodegradability.

[0015] As a preferred embodiment, the anticorrosion and rust inhibitor is selected from one or a combination of triethanolamine, nitrite, benzotriazole, and organic carboxylic acid.

[0016] As a preferred embodiment, the organic carboxylic acid is selected from one or a combination of monobasic acid, dibasic acid, tribasic acid, and polycarboxylic acid.

[0017] As a preferred embodiment, the anticorrosion and rust inhibitor is one or a combination of triethanolamine, nitrite, benzotriazole, sebacic acid, and triazine polycarboxylic acid.

[0018] As a preferred embodiment, the weight ratio of triethanolamine, nitrite, benzotriazole, sebacic acid and triazine polycarboxylic acid is (3-5): (1-3): (0.5-1): (2-3): (1-3).

[0019] As a preferred embodiment, the weight ratio of triethanolamine, nitrite, benzotriazole, sebacic acid and triazine polycarboxylic acid is 4:2:0.5:2.5:2.

[0020] The anti-corrosion and anti-rust system of triethanolamine, nitrite, benzotriazole, sebacic acid and triazine polycarboxylic acid used in the present application has good corrosion resistance for steel, copper and zinc parts, can avoid the shedding of metal coating and extend the service life of the hydraulic support.

[0021] As a preferred embodiment, the complexing agent is a metal sodium salt, and the metal sodium salt is selected from one or a combination of ethylenediaminetetraacetic acid sodium salt, aminotriacetic acid sodium salt, glutamic acid diacetic acid sodium salt, and methylglycine diacetic acid sodium salt.

[0022] As a preferred embodiment, the complexing agent is a combination of glutamic acid diacetic acid sodium salt and methylglycine diacetic acid sodium salt. As a preferred embodiment, the weight ratio of glutamic acid diacetic acid sodium salt and methylglycine diacetic acid sodium salt is 1: (1-2). More preferably, the weight ratio of glutamic acid diacetic acid sodium salt and methylglycine diacetic acid sodium salt is 1: 1.

[0023] The combination of glutamic acid diacetic acid sodium salt and methylglycine diacetic acid sodium salt is used as a complexing agent, which can form a soluble complex with calcium and magnesium ions, avoiding the influence of hard water quality on the stability of the emulsified oil during dilution. The applicant further found that the use of a combined complexing agent can disperse the insoluble organic soap that has been formed, avoiding the precipitation of insoluble impurities and clogging the filter, thereby affecting the operation of the hydraulic support.

[0024] As a preferred embodiment, the defoaming agent is an organic modified siloxane emulsion, and the viscosity of the organic modified siloxane emulsion at 25° C. is 500-2000 cps.

[0025] Using organic modified siloxane emulsion with a viscosity of 500-2000cps as a defoamer can control the foaming tendency and defoaming speed of the emulsified oil, so that the defoamer is evenly dispersed in the emulsified oil, stays stably in the emulsified oil, prolongs the defoaming time, and has a certain anti-foaming effect. At the same time, the presence of organic modified siloxane emulsion can prevent the foam from overflowing the box and causing the leakage and pollution of the emulsified oil, and avoid the influence of foaming on the work of the hydraulic support.

[0026] As a preferred embodiment, the coupling agent is selected from one or a combination of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, and glycerol.

[0027] As a preferred embodiment, the coupling agent is a combination of triethylene glycol monobutyl ether and glycerol.

[0028] As a preferred embodiment, the weight ratio of triethylene glycol monobutyl ether to glycerol is (1-2): (2-3).

[0029] As a preferred embodiment, the weight ratio of triethylene glycol monobutyl ether to glycerol is 1.5:2.5.

[0030] During the experiment, the applicant found that the use of a grease-free concentrated liquid as a hydraulic lubricating material has insufficient lubricating performance in actual use, is prone to rust, and causes rapid wear of sealing materials. The lubrication effect can be improved by introducing synthetic esters, and under the conditions of a combined coupling agent of triethylene glycol monobutyl ether and glycerol, the environmental degradability is significantly improved, and the use effect is stable. The reason may be that triethylene glycol monobutyl ether and glycerol can couple the oil and water phases in the emulsified oil stock solution, and form a relatively thermodynamically stable homogeneous system under the joint action of surfactants. It is also stable under high and low temperature environments. The emulsified oil can return to its original state after repeated low-temperature solidification and room-temperature thawing, and can remain stable in long-term storage under harsh environments.

[0031] The second aspect of the present invention provides a method for preparing a rapidly biodegradable emulsified oil for a hydraulic support, comprising the following steps:

[0032] The raw materials are mixed according to weight, heated and stirred continuously, and the mixture is obtained after being mixed evenly.

[0033] As a preferred embodiment, the heating temperature is 40-60° C., the stirring rate is 150-250 rpm, and the stirring time is 100-150 min.

[0034] As a preferred embodiment, the heating temperature is 45-55°C, the stirring rate is 200 rpm, and the stirring time is 120 min.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) The rapidly biodegradable emulsified oil for hydraulic supports of the present invention can improve the biodegradability of the emulsified oil by using isooctyl oleate as the synthetic ester. The average biodegradation rate of the present invention in the 10-day window period detected by OECD 301E is as high as 78.88%, and the average biodegradation rate on the 28th day is 82.74%, which exceeds the passing level of ≥70% for rapidly biodegradable chemicals stipulated in OECD 301. At the same time, the present invention has good lubricity, and its stability and hydrolysis stability are better than those of natural animal and plant oils and fats.

[0037] (2) The rapidly biodegradable emulsified oil for hydraulic supports of the present invention uses a combination of sodium glutamate diacetate and sodium methylglycine diacetate as a chelating agent, which can dissolve calcium and magnesium ions in water, disperse the insoluble organic soaps that have been formed, protect the stability of the emulsified oil, and prevent the precipitation of impurities from affecting the normal operation of the hydraulic equipment.

[0038] (3) The rapidly biodegradable emulsified oil for hydraulic supports of the present invention uses a combination of triethylene glycol monobutyl ether and glycerol as a coupling agent, so that the emulsified oil can maintain its original state after being solidified at low temperature and thawed at room temperature, and can be stored for a long time. DETAILED DESCRIPTION

[0039] Example 1

[0040] A rapidly biodegradable emulsified oil for hydraulic supports. The raw materials for its preparation include, by weight, 10 parts of synthetic ester, 12 parts of surfactant, 11 parts of anticorrosion and rust inhibitor, 6 parts of complexing agent, 2 parts of bactericide, 0.05 parts of defoaming agent, 4 parts of coupling agent and 55 parts of deionized water.

[0041] The synthetic ester is isooctyl oleate.

[0042] The surfactant is a combination of tall oil fatty acid ALTAPYNE M-28B, triethanolamine, fatty alcohol polyoxyethylene ether carboxylic acid EMULSOGEN COA 070, fatty alcohol polyoxyethylene ether MARLOSOL TA 60, and fatty acid ester polyoxyethylene ether PEG-600DO, with a weight ratio of 4:4:1:1:2.

[0043] The anticorrosion and rust inhibitor is a combination of triethanolamine, nitrite, benzotriazole, sebacic acid, and triazine polycarboxylic acid, with a weight ratio of 4:2:0.5:2.5:2. The triazine polycarboxylic acid is purchased from BASF and the model is IRGACOR L190.

[0044] The complexing agent is a combination of glutamic acid diacetic acid sodium salt and methylglycine diacetic acid sodium salt, with a weight ratio of 1:1.

[0045] The defoaming agent is an organic modified siloxane emulsion, the viscosity of the organic modified siloxane emulsion at 25° C. is 500-2000 cps, and the defoaming agent is purchased from Mengqingxin, and the model is FOAM BAN 1875.

[0046] The coupling agent is a combination of triethylene glycol monobutyl ether and glycerol, with a weight ratio of 1.5:2.5.

[0047] The bactericide is s-triazine.

[0048] A method for preparing a rapidly biodegradable emulsified oil for a hydraulic support comprises the following steps:

[0049] The raw materials are mixed according to weight, heated and stirred continuously, and the mixture is obtained after being mixed evenly.

[0050] The heating temperature was 50°C, the stirring rate was 200 rpm, and the stirring time was 120 min.

[0051] Example 2

[0052] A rapidly biodegradable emulsified oil for hydraulic supports and a preparation method thereof, wherein the specific steps are the same as those of Example 1, except that the synthetic ester is replaced by 7# mineral oil.

[0053] Example 3

[0054] A rapidly biodegradable emulsified oil for hydraulic supports and a preparation method thereof, wherein the specific steps are the same as those of Example 1, except that the synthetic ester is replaced by rapeseed oil.

[0055] Example 4

[0056] A rapidly biodegradable emulsified oil for hydraulic supports and a preparation method thereof. The specific steps are the same as those of Example 1, except that the anticorrosion and rust inhibitor is a combination of triethanolamine, nitrite, benzotriazole, sebacic acid, and triazine polycarboxylic acid in a weight ratio of 4:2:0.5:1:4.

[0057] Example 5

[0058] A rapidly biodegradable emulsified oil for hydraulic supports and a preparation method thereof, wherein the specific steps are the same as those of Example 1, except that the coupling agent is a combination of triethylene glycol monobutyl ether and glycerol, with a weight ratio of 0.5:4.

[0059] Performance Testing

[0060] The emulsified oils for hydraulic supports prepared in Examples 1-5 were tested according to the industry standard MT 76-2011 “Emulsified oils, concentrated solutions and high water content hydraulic fluids for hydraulic supports”. The test results are shown in Table 1.

[0061] Table 1

[0062]

[0063]

Claims

1. A rapidly biodegradable emulsified oil for hydraulic support, characterized in that: The raw materials for preparation include, by weight: 2.0-12.0 parts of synthetic ester, 3.0-15.0 parts of surfactant composition, 4.0-15.0 parts of anticorrosion and rust inhibitor, 2.0-8.0 parts of complexing agent, 1.0-3.0 parts of bactericide, 0.01-0.50 parts of defoaming agent, 1.0-10.0 parts of coupling agent, and 50.0-70.0 parts of deionized water; The synthetic ester is isooctyl oleate; The complexing agent is a combination of glutamic acid diacetic acid sodium salt and methylglycine diacetic acid sodium salt, with a weight ratio of 1: (1-2); The defoamer is an organic modified siloxane emulsion, and its viscosity at 25° C. is 500-2000 cps; The coupling agent is a combination of triethylene glycol monobutyl ether and glycerol in a weight ratio of (1-2): (2-3); The anticorrosion and rust preventive agent is one or a combination of triethanolamine, nitrite, benzotriazole, sebacic acid, and triazine polycarboxylic acid; The weight ratio of triethanolamine, nitrite, benzotriazole, sebacic acid and triazine polycarboxylic acid is (3-5): (1-3): (0.5-1): (2-3): (1-3); The surfactant composition is a combination of tall oil fatty acid ALTAPYNE M-28B, triethanolamine, fatty alcohol polyoxyethylene ether carboxylic acid EMULSOGEN COA 070, fatty alcohol polyoxyethylene ether MARLOSOL TA 60, and fatty acid ester polyoxyethylene ether PEG-600DO.

2. A method for preparing the rapidly biodegradable emulsified oil for hydraulic support according to claim 1, characterized in that: The following steps are involved: The raw materials are mixed according to weight, heated and stirred continuously, and the mixture is obtained after being mixed evenly.

3. The method for preparing the rapidly biodegradable emulsified oil for hydraulic support according to claim 2, characterized in that: The heating temperature is 40-60° C., and the stirring parameters are: stirring rate 150-250 rpm, and stirring time 100-150 min.

Images